Si le cycle du thorium possède plusieurs avantages par rapport au cycle U/Pu, notamment une meilleure régénération de la matière fissile en spectre thermique et une production moindre d'actinides mineurs, il présente plusieurs limites. L'une d'elles est la présence, dans le combustible thorié irradié, d'232U. Cet isotope est le précurseur d'un rayonnement γ de 2.6 MeV. Cette thèse a, en partie, pour objectif d'étudier les différents paramètres influençant la synthèse de ce noyau dans divers types de combustibles et de réacteurs.L'autre partie de ce travail consiste à estimer l'impact de cet indésirable sur la radioprotection de l'aval du cycle. Dans ce but, un ensemble d'outils, permettant le calcul des spectres énergétiques des différents rayonnements émis par la matière radioactive, a été spécialement développé. Ces outils, dont la véracité a été éprouvée par l'intermédiaire de plusieurs benchmarks, fait partie intégrante de ce travail de thèse. / The thorium cycle is a good candidate for replacing the current U/Pu cycle since the fissile nucleus of the cycle, 233U, has neutronic properties favourable to a much better regeneration of fissile material in thermal reactors. Moreover, the production of minor actinides is significantly reduced. However, the use of Thorium is only viable if the spent fuel is reprocessed to recover the fissile 233U that does not exist in nature. This reprocessing will involve a heavy industrial infrastructure, particularly since thorium based spent fuel contains small quantities of 232U that is the mother of the hard gamma emitter (208Tl) of 2.6 MeV. The goal of this thesis is, firstly, to study the parameters related to the synthesis of 232U in several kind of fuels and reactors. In a second part, the thesis focuses on the impact on radioprotection of the back end of the fuel in case of switching from the current uranium (U/Pu) cycle to the thorium (Th/U) cycle. For this last purpose, CHARS (CHAracterization of Radioactives Sources) was developed during this thesis. This code, validated by several benchmarks, handles the calculation of radiation sources in all aspects of the fuel cycle.

The main focus of this diploma thesis is the utilization of spent coffee ground (SCG) and its biorefinery products in agriculture primarly as a prospective organic fertilizer. The study verifies an influence of the addition of native SCG as well as its acid hydrolysed, defatted and oxidized forms to experimental clay soil on chemical and physical properties (ph, conductivity and mineral content). Growing experiments were realized by using Lactuca sativa to detect positive or negative effects on growth. Samples of basic soil and soil with the addition of commercial NPK fertilizer served as a reference to measuring data. Measurements showed that addition of SCG and products of its biorefinery to the soil caused a decrease of pH and an increase of conductivity of soil samples. Significant increase of extractable calcium, magnesium, manganese and moderate increase of potassium content was detected. 2 % addition of SCG to soil had no impact on plants growth. The number and visual appearance of lettuces were comparable with plants in basic soil. No seed on acid hydrolysed samples germinated, which was caused by an increase of conductivity and sulphate content in these samples. In defatted and oxidized samples the early germination and the highest number of lettuces was observed. The low content of phosphorus in all soil samples had a great impact on growth rate and visual appearance of cultivated lettuces. In comparison with soil with NPK addition, lettuces in samples with SCG and its form had a pink-grey colour and lower growth.

Coffee grounds are one of the very valuable lignocellulosic wastes that have been able to be processed and used for isolated phenolic substances. Many phenolic substances isolated from lignocellulosic wastes have antimicrobial properties. Aim of this thesis is isolation phenolic substances from spent coffee grounds extract and their available antimicrobial properties. Two isolation ways were applied to receive phenolic substances from spent coffee grounds: 1) solvent extraction (hexane, 75% ethanol, 70% acetone, diethyl ether, and ethyl acetate) and 2) release of active substances by alcoholic fermentation. All isolated materials were characterized by the viewpoint of concentration of reducing sugars, polyphenols and flavonoids. Subsequently, their antimicrobial activity was determined by using agar diffusion and broth dilution methods. Two gram-positive bacteria (Bacillus subtilis and Micrococcus luteus), one gram-negative bacteria (Serratia marcescens) and two yeasts (Candida glabrata and Saccharomyces cerevisiae) were used for antimicrobial testing. High-performance liquid chromatography (HPLC) was used to identify phenolic substances in the extracts. First, the results showed that the isolated sample with the highest antimicrobial activity was 70% acetone extract. This extract contained chlorogenic acid, gallic acid, caffeic acid and coumaric acid according to HPLC. The ethyl acetate extract showed the lowest antimicrobial activity. Second, after lyophilization, the isolated materials also revealed high antimicrobial activity. The highest antimicrobial activity displayed the materials obtained by the extraction with 70% ethanol. This sample contained chlorogenic acid, gallic acid and caffeic acids. Next, samples with phenolic compounds were obtained by the alcoholic fermentation of spent coffee grounds. These samples showed similarly to the previous solution extracts significant antimicrobial activity. Interestingly, the unfiltered samples received directly after alcoholic fermentation also showed antifungal properties. The characterization of phenolic compounds by HPLC showed similarly as in previous examples that chlorogenic, caffeic and gallic acids were present in these samples.

This master´s thesis deals with the utilization of spent grains. It briefly introduces the issue of hydraulic transport settling and non-settling mixtures, pumps, piping design and technology designed for a particular case. After these chapters, the calculations of parts of the technology utilization spent grains follow.

This work deals with questions of spent fuel storage casks thermal and physical properties investigation. Foundations of mathematics which are necessary for describing field of temperature are included. The work itself contains calculation methods which are split into two parts. The first one deals with simplified analytic solution and the second part solves the whole problem by the numerical computation.

Master of Science

NR 20140805

Oxidative dissolution of std. UO2 and UO2 doped with Cr2O3 and Al2O3, i.e. ADOPT, induced by H2O2 and γ radiation has been the main focus in this licentiate thesis. The catalytic decomposition of H2O2 on oxides like Gd2O3, HfO2, CeO2, Fe2O3 and CuO were also investigated. A kinetic study was performed by determining first and second order rate constants together with Arrhenius parameters for the decomposition of H2O2. The reactivity of H2O2 towards the oxides mentioned was observed to differ significantly despite their similarities. In the mechanistic study, the yields and dynamics of the formation of the intermediate hydroxyl radical from the decomposition of H2O2 was determined for the oxides and found to differ considerably. A turnover point could be found for most of oxides studied, i.e. an increase in the rate of hydroxyl radical scavenging after a specific amount of consumed H2O2. The reactivity of the std. UO2 and ADOPT towards H2O2 was similar to what was observed for other UO2-based materials in previous studies. The oxidative dissolution in radiation experiments showed a slight but significant difference. This was attributed to a difference in exposed surface area instead of an effect of doping. The difference in oxidative dissolution yield was too small to be significant which supports the previous conclusion. Leaching experiments using spent nuclear fuel were also performed on the two types of fuel showing the same behavior as the unirradiated pellets, i.e., a slightly lower 238U release from ADOPT. The difference was attributed to difference in exposed surface area. The release of fission products with low UO2 solubility displayed a higher release from ADOPT which was attributed to a difference in matrix solubility. Cs was released to a larger extent from std. UO2. This is attributed to the larger grain size of ADOPT, extending the diffusion distance. The release of lanthanides and actinides was slightly higher for the conventional UO2, nevertheless the difference was relatively small. / <p>QC 20140527</p>

No description available.

Denna licensiatavhandling behandlar oxidativ upplösning av UO2. Upplösning av UO2 studeras huvudsakligen då UO2-matrisen hos använt kärnbränsle förväntas fungera som en barriär mot frigörande av radionuklider i ett framtida djupförvar. Lösligheten av U(IV) är mycket låg under i djupförvaret rådande förhållanden emedan U(VI) har betydligt högre löslighet. Oxidation av UO2-matrisen kommer därför att påverka dess löslighet och därmed dess funktion som barriär. I denna avhandling studeras den relativa effektiviteten av en- och två-elektronoxidanter för upplösning av UO2. Vid låga oxidantkoncentrationer är utbytet för upplösningen för en-elektronoxidanter signifikant lägre än för två-elektronoxidanter. För en-elektronoxidanter ökar dock utbytet med ökande oxidanthalt, vilket kan förklaras av den ökade sannolikheten för två konsekutiva en-elektronoxidationer av samma reaktionssite och den ökade möjligheten till disproportionering. Radikaler och molekylära radiolysprodukters relativa inverkan på oxidativ upplösning av UO2 studeras också i denna avhandling genom mätning av mängden upplöst U(VI) i γ-bestrålade system som dominerades av olika oxidanter. Dessa studier visade att upplösningshastigheten av UO2 kan uppskattas från oxidantkoncentrationer framtagna genom simuleringar av radiolys i motsvarande homogena system och hastighetskonstanterna för ytreaktionerna. Simuleringarna visar att de molekylära oxidanterna kommer vara de viktigaste oxidanterna i alla system i denna studie vid långa bestrålningstider (&gt;10 timmar). Vid liknande simuleringar av α-bestrålade system fanns att vid förhållanden relevanta för ett djupförvar för använt kärnbränsle, är det endast de molekylära oxidanterna (i huvudsak H2O2) som är av betydelse för upplösningen av bränslematrisen. Då använt kärnbränsle innehåller en mängd radionuklider som utsätter UO2-matrisen för kontinuerlig bestrålning, är det av vikt att undersöka hur bestrålning påverkar reaktiviteten av UO2. Bestrålningseffekten på reaktionen mellan UO2 och MnO4- studerades. Dessa försök visade att bestrålning av UO2 vid doser &gt;40 kGy leder till att reaktiviteten ökar upp till 1.3 gånger reaktiviteten av obestrålad UO2. Den ökade reaktiviteten kvarstår efter bestrålningen och effekten kan därför möjligen tillskrivas permanenta förändringar i materialet. Vid uppskattning av reaktiviteten hos använt kärnbränsle måste hänsyn tas till denna effekt då bränslet redan efter ett par dagar i reaktor blivit utsatt för doser &gt;40 kGy. Det har tidigare föreslagits att hastigheten för en heterogen västka/fast-fas reaktion är beroende av partikelstorleken hos det fasta materialet, vilket har studerats för UO2-partiklar i denna avhandling. Experimentellt bestämda kinetiska parametrar jämförs med de föreslagna ekvationerna för fyra storleksfraktioner av UO2-pulver och en UO2-pellet. Studien visade partikelstorleksberoendet av andra ordningens hastighetskonstant och aktiveringsenergin för oxidation av UO2 med MnO4- beskrivs relativt väl av de föreslagna ekvationerna. / The general subject of this thesis is oxidative dissolution of UO2. The dissolution of UO2 is mainly investigated because of the importance of the UO2 matrix of spent nuclear fuel as a barrier against radionuclide release in a future deep repository. U(IV) is extremely insoluble under the reducing conditions prevalent in a deep repository, whereas U(VI) is more soluble. Hence, oxidation of the UO2-matrix will affect its solubility and thereby its function as a barrier. In this thesis the relative efficiency of one- and two electron oxidants in dissolving UO2 is studied. The oxidative dissolution yield of UO2 was found to differ between one- and two-electron oxidants. At low oxidant concentrations the dissolution yields for one-electron oxidants are significantly lower than for two-electron oxidants. However, the dissolution yield for one-electron oxidants increases with increasing oxidant concentration, which could be rationalized by the increased probability for two consecutive one-electron oxidations at the same site and the increased possibility for disproportionation. Furthermore, the relative impact of radical and molecular radiolysis products on oxidative dissolution of UO2 is investigated. Experiments were performed where the amount of dissolved U(VI) was measured in γ-irradiated systems dominated by different oxidants. We have found that the UO2 dissolution rate in systems exposed to γ-irradiation can be estimated from oxidant concentrations derived from simulations of radiolysis in the corresponding homogeneous systems and rate constants for the surface reactions. These simulations show that for all systems studied in this work, the molecular oxidants will be the most important oxidants for long irradiation times (&gt;10 hours). Similar simulations of α-irradiated systems show that in systems relevant for a deep repository for spent nuclear fuel, only the molecular oxidants (mainly H2O2) are of importance for the dissolution of the fuel matrix. The effect on UO2 reactivity by irradiation of the material is of importance when predicting the spent fuel dissolution rate since the fuel, due to its content of radionuclides, is exposed to continuous self-irradiation. The effect of irradiation on the reaction between solid UO2 and MnO4- in aqueous solutions was studied. It was found that irradiation of UO2 at doses &gt;40 kGy increases the reactivity of the material up to ~1.3 times the reactivity of unirradiated UO2. The increased reactivity remains after the irradiation and can possibly be attributed to permanent changes in the material. This issue must be taken into account when predicting the reactivity of spent nuclear fuel since the fuel is exposed to doses &gt;40 kGy after only a few days in the reactor. It has earlier been suggested that the rate of a heterogeneous liquid-solid reaction depends on the size of the solid particles. This was investigated for UO2 particles in this thesis. Experimental kinetic parameters are compared to the previously proposed equations for UO2 powder of four size fractions and a UO2 pellet. We have found that the particle size dependence of the second order rate constant and activation energy for oxidation of UO2 by MnO4- is described quite well by the proposed equations. / QC 20101123